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Nonadiabatic Electron Transfer at Metal Surfaces

Gosavi, Shachi and Marcus, R. A. (2000) Nonadiabatic Electron Transfer at Metal Surfaces. Journal of Physical Chemistry B, 104 (9). pp. 2067-2072. ISSN 1520-6106. doi:10.1021/jp9933673.

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The present article treats the role of the density of electronic states ρ_F at the Fermi level of a metal in affecting the rate of nonadiabatic electron transfer. The rate constant k_(ET) is calculated for the electron transfer across an alkanethiol monolayer on platinum and on gold. The ρ_F of platinum is about 7.5 times that of gold, the difference being mainly due to the d band of Pt. In spite of this difference, the electron transfer rate constant k_(ET) calculated in the present paper increases only by a factor of about 1.8, instead of the factor of about 7.5 expected using ρ_F alone. Implications of these results for present and past experiments are described. Bands which are weakly coupled (e.g., the d-band of Pt in the present case) contribute much less to the rate constant than is suggested by their density of states ρ_F. Thereby, k_(ET) is approximately independent of ρ_F in two cases: (1) adiabatic electron transfer and (2) nonadiabatic electron transfer when the extra ρ_F is due to the d electrons. Experiments which can test the latter are discussed.

Item Type:Article
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URLURL TypeDescription DOIArticle
Marcus, R. A.0000-0001-6547-1469
Additional Information:© 2000 American Chemical Society. Received: September 21, 1999. Published on Web 02/12/2000. We thank Professors Finklea and Forster for insightful discussions and kindly sharing their data with us. It is a pleasure to acknowledge the support of this research by the National Science Foundation and the Office of Naval Research.
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Office of Naval Research (ONR)UNSPECIFIED
Issue or Number:9
Record Number:CaltechAUTHORS:20150316-132413291
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Official Citation:Nonadiabatic Electron Transfer at Metal Surfaces Shachi Gosavi and and R. A. Marcus The Journal of Physical Chemistry B 2000 104 (9), 2067-2072 DOI: 10.1021/jp9933673
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:55797
Deposited By: Tony Diaz
Deposited On:16 Mar 2015 21:12
Last Modified:10 Nov 2021 20:50

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